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Title: Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water

Abstract

Efficient removal of pertechnetate (TcO4-) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4- anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metal-organic framework can adsorb perrhenate (ReO4-) anions, a non-radioactive sur-rogate for TcO4-, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4- (surrogate for TcO4-) molecule within the framework.

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Environmental Management (EM)
OSTI Identifier:
1340749
Report Number(s):
PNNL-SA-116173
Journal ID: ISSN 0020-1669; 830403000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 55; Journal Issue: 17
Country of Publication:
United States
Language:
English
Subject:
Pertechnetate removal; MOFs

Citation Formats

Banerjee, Debasis, Xu, Wenqian, Nie, Zimin, Johnson, Lewis E. V., Coghlan, Campbell, Sushko, Maria L., Kim, Dongsang, Schweiger, Michael J., Kruger, Albert A., Doonan, Christian J., and Thallapally, Praveen K.. Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b01004.
Banerjee, Debasis, Xu, Wenqian, Nie, Zimin, Johnson, Lewis E. V., Coghlan, Campbell, Sushko, Maria L., Kim, Dongsang, Schweiger, Michael J., Kruger, Albert A., Doonan, Christian J., & Thallapally, Praveen K.. Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water. United States. doi:10.1021/acs.inorgchem.6b01004.
Banerjee, Debasis, Xu, Wenqian, Nie, Zimin, Johnson, Lewis E. V., Coghlan, Campbell, Sushko, Maria L., Kim, Dongsang, Schweiger, Michael J., Kruger, Albert A., Doonan, Christian J., and Thallapally, Praveen K.. 2016. "Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water". United States. doi:10.1021/acs.inorgchem.6b01004.
@article{osti_1340749,
title = {Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water},
author = {Banerjee, Debasis and Xu, Wenqian and Nie, Zimin and Johnson, Lewis E. V. and Coghlan, Campbell and Sushko, Maria L. and Kim, Dongsang and Schweiger, Michael J. and Kruger, Albert A. and Doonan, Christian J. and Thallapally, Praveen K.},
abstractNote = {Efficient removal of pertechnetate (TcO4-) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4- anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metal-organic framework can adsorb perrhenate (ReO4-) anions, a non-radioactive sur-rogate for TcO4-, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4- (surrogate for TcO4-) molecule within the framework.},
doi = {10.1021/acs.inorgchem.6b01004},
journal = {Inorganic Chemistry},
number = 17,
volume = 55,
place = {United States},
year = 2016,
month = 9
}
  • Efficient removal of pertechnetate (TcO4 -) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4 - anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stablemore » zirconium based metalorganic framework can adsorb perrhenate (ReO4 -) anions, a non-radioactive surrogate for TcO4 -, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4 - (surrogate for TcO4 -) molecule within the framework.« less
  • We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2)g(-1); to our knowledge, currently the highest published for Zr-based MOFs. CH4/CO2/H-2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 gg(-1), which corresponds to 43 gL(-1). The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 v(STP)/v and 0.27 gg(-1), respectively.
  • At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO 4–) because of the ion’s volatility, thereby requiring a different remediation method for this long-lived (t 1/2 = 2.1 × 10 5 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr 6-based metal–organic framework (MOF), NU-1000, to capture perrhenate (ReOmore » 4–), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal X-ray diffraction indicates both chelating and nonchelating perrhenate binding motifs are present in both the small pore and the mesopore of NU-1000. Postadsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) further elucidates the uptake mechanism and powder X-ray diffraction (PXRD) and Brunauer–Emmett–Teller (BET) surface area analysis confirm the retention of crystallinity and porosity of NU-1000 throughout adsorption.« less
  • The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achievedmore » by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5 mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments revealed significantly high microporosity. • The material showed high adsorption selectivity for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions.« less